CN110354898A - Polyvinyl alcohol catalysis composite membrane of functionalization and preparation method thereof - Google Patents
Polyvinyl alcohol catalysis composite membrane of functionalization and preparation method thereof Download PDFInfo
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- CN110354898A CN110354898A CN201910602392.1A CN201910602392A CN110354898A CN 110354898 A CN110354898 A CN 110354898A CN 201910602392 A CN201910602392 A CN 201910602392A CN 110354898 A CN110354898 A CN 110354898A
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- solution
- acid
- pva
- polyvinyl alcohol
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 68
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 68
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 18
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 8
- 229940068984 polyvinyl alcohol Drugs 0.000 claims abstract description 67
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000661 sodium alginate Substances 0.000 claims abstract description 22
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 22
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 60
- 235000019441 ethanol Nutrition 0.000 claims description 40
- 238000005886 esterification reaction Methods 0.000 claims description 17
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 15
- 230000032050 esterification Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000008595 infiltration Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 claims 1
- 239000000783 alginic acid Substances 0.000 claims 1
- 229960001126 alginic acid Drugs 0.000 claims 1
- 229920000615 alginic acid Polymers 0.000 claims 1
- 150000004781 alginic acids Chemical class 0.000 claims 1
- MVIOINXPSFUJEN-UHFFFAOYSA-N benzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=CC=C1 MVIOINXPSFUJEN-UHFFFAOYSA-N 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 230000000149 penetrating effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 229920001607 Policresulen Polymers 0.000 description 4
- ACZKMKGNTMOPBD-UHFFFAOYSA-N policresulen Chemical compound CC1=CC(O)=C(S(O)(=O)=O)C=C1CC1=CC(S(O)(=O)=O)=C(O)C(CC=2C(=CC(O)=C(C=2)S(O)(=O)=O)C)=C1C ACZKMKGNTMOPBD-UHFFFAOYSA-N 0.000 description 4
- 229960002954 policresulen Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the polyvinyl alcohol of a kind of functionalization catalysis composite membranes and preparation method thereof.It is characterized in that the catalysis composite membrane be double-layer structure: separating layer by after being crosslinked polyvinyl alcohol (PVA) and sodium alginate (SA) form, Catalytic Layer by acidic catalyst be crosslinked PVA form.Its specific preparation method: crosslinking agent is added after PVA and SA solution is mixed and is crosslinked, then knifing, dries；After mixing by PVA and pretreated acidic catalyst, crosslinking agent is added, forms casting solution, is then coated in separating layer, prepares Catalytic Layer using dipping phase inversion.The present invention is grafted acidic catalyst in PVA long-chain, so that achieving the purpose that fixed catalyst by chemical graft process.And the present invention is handled composite membrane using dipping phase inversion, moisture is reduced in Catalytic Layer to the greatest extent to isolated destruction, and also will form porous structure, reduces the resistance to mass tranfer that moisture removes in reaction, active site is also increased, the quasi- rate of acetic acid is improved.
Description
Technical field
The invention belongs to the polyvinyl alcohol catalysis of materialogy field and technical field of membrane separation, in particular to functionalization is compound
Film and preparation method thereof.Polyvinyl alcohol catalysis composite membrane prepared by the present invention is mainly used for organic carboxyl acid and the esterification of Organic Alcohol is anti-
It answers.
Background technique
Ethyl acetate tool have been widely used, such as be used as industrial solvent, can be used for coating, adhesive, malthoid colorant,
Staple fibre etc.；As adhesive, it can be used for the production of olivet；As extractant, it can be used for the life of the products such as organic acid
It produces；As spice material, it can be used for the primary raw material of the fragrance such as the fruit essences such as pineapple, banana, strawberry and cream.
Ethyl alcohol and acetic acid synthesizing ethyl acetate and by-product water under acidic catalyst effect.Esterification be one by
The reaction of thermodynamical equilibrium control.In order to improve the conversion ratio of acetic acid, this needs to break chemical reaction equilibrium limitation, and making can be converse
It should be mobile to product side.For the limitation for breaking reversible reaction, the conversion ratio of acetic acid is improved, we can carry out in terms of two
Consider；First, increasing the content of reaction side ethyl alcohol；Second, by-product moisture is removed outside reaction system in time, keep balance positive
It carries out.The former be in general traditional industry frequently with method, the latter be in the modern industry frequently with a kind of technology --- seep
Vaporization thoroughly.
It is an excellent selection using Pervaporation Technology.Because it, which is less than, generally passes through reaction from cost consideration
Moisture is removed in distillation；Consider that it does not affect reactant and target product from reaction system.
Infiltration evaporation (PV) is a kind of membrane separation technique.PV is driving using feed liquid film upstream and downstream component chemical potential difference
Power realizes mass transfer, realizes selectivity to the difference of different component compatibility and resistance to mass tranfer in feed liquid using film.We answer PV
With in the esterification reaction, to break the limitation of chemical balance, the yield of esterification is improved.
Composite membrane is applied in the esterification reaction, there are some reports.Chinese patent CN102958586B report one
The catalytic membrane and preparation method thereof of kind catalytic esterification, for the catalysis composite membrane using non-woven fabrics as basement membrane, solid acid is to urge
Agent coats Catalytic Layer casting solution in the hole and gap of nonwoven surface and non-woven fabrics fiber, is then crosslinked.Composite membrane is answered
In the preparation of catalytic esterification and biodiesel, the conversion ratio of ethyl acetate is less than 80%, and fatty acid methyl ester conversion rate is about
Between 90-96%.One layer of this film is dual-purpose, that is, has and be catalyzed and separate two kinds of effects, be a very interesting trial, still
Catalytic Layer is more coarse, and the moisture generated in esterification will lead to hydrophilic polymer and slowly be swollen, and will lead to point of film
Decline from performance, the substance in reaction system is caused to be lost by film, this can gradually lose the application of film in the reaction.
Poly- cresol sulfonic acid is large drug, inexpensive easy, nontoxic, has huge potentiality in catalyst application aspect.And
And Policresulen contains sulfonic group and hydroxyl, sulfonic group can provide hydrogen ion, the catalyst as esterification；Hydroxyl can
To be grafted with other substances, achieve the purpose that fixed catalyst.PVA is compared to other hydrophilic filmogens, the function of molecule
Group is relatively simple, can accommodate complicated catalyst solution, be not easy with various catalyst reactions, be apply it is exhausted in Catalytic Layer
Good material.
Dipping phase inversion is a kind of method for the novel preparation catalytic membrane being concerned recent years.Due to this method
The film surface prepared is loose and porous structure, the moisture in Catalytic Layer can be made to be replaced out, and catalyst is fixed
On PVA, the loss of catalyst can be reduced.And after ethyl alcohol impregnates, can flow out small part it is non-grafted on catalysis
Agent prevents catalyst from flowing in reactor, corrosion reaction device.The prepared double-deck catalysis composite membrane, can be greatly improved second
The conversion ratio of acid.
Summary of the invention
The purpose of the invention is to the polyvinyl alcohol catalysis for improving the deficiency of previous catalytic membrane and preparing functionalization is compound
Film, it is a further object of the present invention to provide the preparation methods of above-mentioned polyvinyl alcohol catalysis composite membrane.It is prepared using the method
Catalysis composite membrane has the characteristics that catalytic activity is high, separating property is good, low in cost and esterification yield is high, therefore in the esterification reaction
With great application prospect.
Technical solution of the present invention: the polyvinyl alcohol of functionalization is catalyzed composite membrane, it is characterised in that the composite membrane is bilayer
Structure: separating layer by after being crosslinked polyvinyl alcohol (PVA) and sodium alginate (SA) form, Catalytic Layer is by the acidity after being crosslinked
Catalyst and polyvinyl alcohol (PVA) composition；The ethanol water that disintegrate-quality score is 90%, permeation flux 104-
200gm-2·h-1, separation factor 106-1940；Applied to catalysis acetic acid in infiltration evaporation catalytic film reactor and ethyl alcohol esterification
12h, acetic acid conversion 90-96% are reacted in reaction.
It is preferred that the acidic catalyst is poly- cresol sulfonic acid or p-hydroxybenzenyl sulfonate.
The present invention also provides a kind of methods for preparing above-mentioned sulfonated polyethylene alcohol catalysis composite membrane, and specific steps are such as
Under:
(1) pretreatment of catalyst；By acidic catalyst agent solution, nanoparticle and ethyl alcohol, it is mixed to be put into ultrasound in ultrasonic device
It closes uniformly, is then placed in Rotary Evaporators revolving to sticky, takes out stand-by；
(2) preparation of separating layer: preparation mass concentration is 3-7% polyvinyl alcohol (PVA) solution and mass concentration is 1-3%
Sodium alginate (SA) solution, take polyvinyl alcohol (PVA) and sodium alginate (SA) solution to be uniformly mixed, stirred after crosslinking agent is added
It mixes, filters, standing and defoaming obtains casting solution；Using automatic knifing machine, casting solution is poured slowly on glass plate, knifing is coated, sets
In filter, dry at room temperature stand-by；
(3) preparation of Catalytic Layer: preparing polyvinyl alcohol (PVA) solution that mass concentration is 5-10%, will be pre- in step (1)
Treated, and acidic catalyst is added in polyvinyl alcohol (PVA) solution, is stirred evenly, standing and defoaming, and crosslinking agent stirring is added,
It using knifing machine, is coated in the separating layer of step (2) preparation, is put into straight alcohol solution and impregnates, taking-up is dried stand-by.
Nanoparticle described in preferred steps (1) is nano silica, nano-titanium dioxide or nano zirconium dioxide；
The acidic catalyst agent solution is poly- cresol sulfonic acid solution or p-hydroxybenzenyl sulfonate solution；The quality of acidic catalyst agent solution is dense
Degree is 55%~65%.
The mass ratio of nanoparticle described in preferred steps (1) and catalyst solution is 0.1-0.2；Ethyl alcohol and catalyst
Solution quality ratio is 0.5-1；It is 60-80 DEG C that temperature is rotated in Rotary Evaporators.
Polyvinyl alcohol (PVA) solution and sodium alginate (SA) solution quality ratio are (0.4-2.35) in preferred steps (2): 1.
Crosslinking agent is the mixture of glutaraldehyde and acid in preferred steps (2), and wherein the mass ratio of glutaraldehyde and acid is 1:
(0.25-1)；Acid is sulfuric acid hydrochloric acid；The additional amount of crosslinking agent is that the addition quality of control glutaraldehyde is polyvinyl alcohol (PVA) and sea
The 0.05-0.2% of mosanom (SA) mixed solution quality
Mixing time is 6-24h after crosslinking agent is added in preferred steps (2).
Crosslinking agent described in preferred steps (3) is glutaraldehyde, maleic acid or citric acid；The addition quality of crosslinking agent is
The 0.05-1.7% of PVA solution quality；Through (1) treated acidic catalyst additive amount and polyvinyl alcohol (PVA) in step (3)
Molar ratio be 0.1-0.3；It is 0.5-2h that soaking time in straight alcohol solution is put into described in step (3).
Knifing rate in preferred steps (2) and (3) is 5-30mmin-1；It adjusts and scrapes in step (2) and step (3)
The height of knife is 200-700 μm.
The utility model has the advantages that
1) catalysis composite membrane prepared by the present invention has catalytic activity high, and good separating effect and catalytic stability are well etc. special
Point summarizes applied to infiltration evaporation catalytic film reactor, can effectively improve the conversion ratio of esterification,
2) catalysis composite membrane of the invention is double-layer structure, can be realized the purpose for separating water in esterification in situ.It urges
Changing the moisture that layer generates can be separated by separating layer in time, and then esterification is promoted to tilt to positive direction always, therefore
It will increase the conversion ratio of acetic acid, improve esterification yied.
3) present invention prepares Catalytic Layer using dipping phase inversion, and compared to casting method, this method can reduce catalysis
Destruction of the moisture to separating layer in layer, and Catalytic Layer can obtain porous structure, reduce moisture resistance to mass tranfer, increase acidic site
Point.
4) the preparation method of the product of the invention is simple, does not need some special instrument and equipments, and catalyst is inexpensive easy, benefit
It is industrialized in realizing.
Specific embodiment
Further the present invention is illustrated below by specific embodiment, but the present invention is not limited only to this.
Embodiment 1
(1) pretreatment of catalyst；30g Policresulen aqueous solution is weighed, 3g nano silica and 30g ethyl alcohol is added
Solution is put into ultrasound 1h in ultrasonic cleaning machine, is then placed in 80 DEG C of Rotary Evaporators revolving to sticky, takes out stand-by.
(2) preparation of separating layer: the SA solution of 3wt%PVA solution and 3wt% is prepared, 15gPVA and 35gSA solution is taken
(PVA:SA=0.42:1) it is uniformly mixed, glutaraldehyde 0.025g is then added, sulfuric acid 0.025g and 5g water stirs 6h, stands de-
Bubble.Using automatic knifing machine, casting solution is poured slowly on glass plate, knifing, the height for adjusting scraper is 300 μm, knifing speed
Rate is 15mmin-1, it is placed in filter, dries stand-by at room temperature.
(3) preparation of Catalytic Layer: preparing the PVA solution of 5wt%, takes 30g solution, and the catalyst 2g in step (1) is added
Glutaraldehyde 0.03g, stirring, using knifing machine, knifing rate is added into PVA solution in (catalyst be PVA molar ratio 0.1)
For 20mmin-1, the height for adjusting scraper is 500 μm, is coated in separating layer, and inclination, which is slowly put into straight alcohol solution, impregnates
1.5h, taking-up are dried, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 90.6%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g, vacuum in reaction process
Degree maintains 250Pa or so, and bath temperature controls at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, use gas-chromatography
The content of water and ethyl alcohol in reaction solution and penetrating fluid is measured, so that calculating separation factor is 678, flux 108gm-2·h-1。
Embodiment 2
(1) pretreatment of catalyst；30g p-hydroxybenzenyl sulfonate solution is weighed, 6g nano zirconium dioxide and 15g ethyl alcohol is added
Solution is put into ultrasonic cleaning machine ultrasound 2h to mixing, and is then placed in 70 DEG C of Rotary Evaporators revolving to sticky, take out to
With.
(2) preparation of separating layer: the SA solution of 5wt%PVA solution and 1wt% is prepared, 20gPVA and 20gSA solution is taken
(PVA:SA=1:1) it is uniformly mixed, glutaraldehyde 0.04g, sulfuric acid 0.0125g and 5g water is then added, stirring for 24 hours, is filtered, room temperature
Lower standing and defoaming 12h.Using automatic knifing machine, casting solution is poured slowly on substrate, coats knifing, the height for adjusting scraper is
200 μm, knifing rate is 30mmin-1, it is placed in filter, dries stand-by at room temperature.
(3) preparation of Catalytic Layer: preparing the PVA solution of 8wt%, takes 30g solution, and the catalyst in step (1) is added
Citric acid 0.51g, 80 DEG C of stirring 6h are added into PVA solution in 4.38g (catalyst be PVA molar ratio 0.3), and the row of standing steeps,
Using knifing machine, the height for adjusting scraper is 350 μm, and knifing rate is 30mmin-1, it is coated in separating layer, inclination is slow
It is put into straight alcohol solution and impregnates 1h, taking-up is dried, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.With
Content of material in gas Chromatographic Determination reaction solution and penetrating fluid, to calculate the quasi- rate of acetic acid, obtaining reflection 12h conversion ratio is
95.6%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g, vacuum degree is maintained in reaction process
250Pa or so, bath temperature control at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, reacted with gas Chromatographic Determination
The content of water and ethyl alcohol in liquid and penetrating fluid, so that calculating separation factor is 113, flux 126gm-2·h-1。
Embodiment 3
(1) pretreatment of catalyst；30g Policresulen aqueous solution is weighed, 6g nano-titanium dioxide and 15g ethyl alcohol is added
Solution is put into ultrasonic cleaning machine ultrasound 1h to mixing, and is then placed in 60 DEG C of Rotary Evaporators revolving to sticky, take out to
With.
(2) preparation of separating layer: 7wt%PVA solution and 3wt%SA solution are prepared, 35gPVA and 15gSA solution is taken
(PVA:SA=2.33:1) it is uniformly mixed, glutaraldehyde 0.1g is then added, sulfuric acid 0.025g and 5g water stirs 12h, and filtering is quiet
Set deaeration 8h.Using automatic knifing machine, casting solution is poured slowly on substrate, coats knifing, the height for adjusting scraper is 500 μ
M, knifing rate are 20mmin-1, it is placed in filter, dries stand-by at room temperature.
(3) preparation of Catalytic Layer: preparing the PVA solution of 10wt%, takes 30g solution, and the catalyst in step (1) is added
Glutaraldehyde 0.015g stirring is added into PVA solution in 6.015g (catalyst be PVA molar ratio 0.15), using knifing machine, adjusts
The height for saving scraper is 700 μm, and knifing rate is 20mmin-1, it is coated in separating layer, inclination is slowly put into straight alcohol solution
Middle immersion 0.5h, taking-up are dried, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 260Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.With
Content of material in gas Chromatographic Determination reaction solution and penetrating fluid, to calculate the quasi- rate of acetic acid, obtaining reflection 12h conversion ratio is
92.4%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g, vacuum degree is maintained in reaction process
250Pa or so, bath temperature control at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, reacted with gas Chromatographic Determination
The content of water and ethyl alcohol in liquid and penetrating fluid, so that calculating separation factor is 506, flux 179gm-2·h-1。
Case study on implementation 4
(1) pretreatment of catalyst；30g Policresulen aqueous solution is weighed, 6g nano silica and 30g ethyl alcohol is added
Solution is put into ultrasonic cleaning machine ultrasound 1h to mixing, and is then placed in 60 DEG C of Rotary Evaporators revolving to sticky, take out to
With.
(2) preparation of separating layer: 3wt%PVA solution and 3wt%SA solution are prepared, 35gPVA and 15gSA solution is taken
(PVA:SA=2.33:1) it being uniformly mixed, glutaraldehyde 0.075g is then added, sulfuric acid 0.0375g and 5g water stirs 12h, it filters,
Standing and defoaming 4h at 30 DEG C.Using automatic knifing machine, casting solution is poured slowly on substrate, knifing is coated, adjusts the height of scraper
Degree is 700 μm, and knifing rate is 5mmin-1, it is placed in filter, dries stand-by at room temperature.
(3) preparation of Catalytic Layer: preparing the PVA solution of 10wt%, takes 30g solution, and the catalyst in step (1) is added
8.02g (catalyst be PVA molar ratio 0.2) is into PVA solution, after mixing evenly, stands, glutaraldehyde is then added
0.015g, stirring, using knifing machine, the height for adjusting scraper is 200 μm, and knifing rate is 5mmin-1, it is coated in separating layer
On, inclination, which is slowly put into straight alcohol solution, impregnates 2h, and taking-up is dried, for use.
Using ethyl alcohol and acetic acid as reactant, the molar ratio that ethyl alcohol and acetic acid is added is 2:1, and gross mass 10g reacted
Vacuum degree maintains 250Pa or so in journey, and bath temperature controls at 75 DEG C, took a sample at interval of 2 hours, continuously take 6 times.
Reflection 12h is obtained to calculate the quasi- rate of acetic acid with content of material in gas Chromatographic Determination reaction solution and penetrating fluid
Conversion ratio is 93.05%.Using water and ethyl alcohol as reaction system, water content 10%, gross mass 50g is true in reaction process
Reciprocal of duty cycle maintains 250Pa or so, and bath temperature controls at 75 DEG C, took a sample at interval of 1 hour, continuously take 3 times, with gas phase color
The content of water and ethyl alcohol in spectrum measurement reaction solution and penetrating fluid, so that calculating separation factor is 1932, flux 106gm-2·h-1。
Claims (10)
1. the polyvinyl alcohol of functionalization is catalyzed composite membrane, it is characterised in that the composite membrane is double-layer structure: separating layer is by being crosslinked
Rear polyvinyl alcohol and sodium alginate composition, Catalytic Layer by after being crosslinked acidic catalyst and polyvinyl alcohol form；Separate matter
Measure the ethanol water that score is 90%, permeation flux 104-200gm-2·h-1, separation factor 106-1940；It answers
For being catalyzed acetic acid and ethyl alcohol esterification in infiltration evaporation catalytic film reactor, 12h, acetic acid conversion 90-96% are reacted.
2. the polyvinyl alcohol of functionalization is catalyzed composite membrane according to claim 1, it is characterised in that the acidic catalyst
For poly- cresol sulfonic acid or p-hydroxybenzenyl sulfonate.
3. a kind of method for preparing sulfonated polyethylene alcohol catalysis composite membrane as described in the appended claim 1, the specific steps of which are as follows:
(1) pretreatment of catalyst；By acidic catalyst agent solution, nanoparticle and ethyl alcohol, it is equal to be put into ultrasonic mixing in ultrasonic device
It is even, revolving is then placed in Rotary Evaporators to sticky, is taken out stand-by；
(2) preparation of separating layer: the alginic acid that mass concentration is 3-7% poly-vinyl alcohol solution and mass concentration is 1-3% is prepared
Sodium solution takes polyvinyl alcohol and sodium alginate soln to be uniformly mixed, stirs after crosslinking agent is added, filters, and standing and defoaming obtains casting film
Liquid；Using automatic knifing machine, casting solution is poured slowly on glass plate, coat knifing, be placed in filter, dry at room temperature to
With；
(3) preparation of Catalytic Layer: preparing the poly-vinyl alcohol solution that mass concentration is 5-10%, will be pretreated in step (1)
Acidic catalyst is added in poly-vinyl alcohol solution, is stirred evenly, standing and defoaming, and crosslinking agent stirring is added, and using knifing machine, is applied
It overlays in the separating layer of step (2) preparation, is put into straight alcohol solution and impregnates, taking-up is dried stand-by.
4. according to the method described in claim 3, it is characterized in that nanoparticle described in step (1) is nanometer titanium dioxide
Silicon, nano-titanium dioxide or nano zirconium dioxide；The acidic catalyst agent solution is poly- cresol sulfonic acid solution or para hydroxybenzene
Sulfonic acid solutions；The mass concentration of acidic catalyst agent solution is 55%~65%.
5. according to the method described in claim 3, it is characterized in that nanoparticle described in step (1) and catalyst solution
Mass ratio is 0.1-0.2；Ethyl alcohol and catalyst solution mass ratio are 0.5-1；It is 60-80 DEG C that temperature is rotated in Rotary Evaporators.
6. according to the method described in claim 3, it is characterized in that poly-vinyl alcohol solution and sodium alginate soln matter in step (2)
Amount is than being (0.4-2.35): 1.
7. according to the method described in claim 3, it is characterized in that in step (2) crosslinking agent be glutaraldehyde and acid mixture,
Wherein the mass ratio of glutaraldehyde and acid is 1:(0.25-1)；Acid is sulfuric acid hydrochloric acid；The additional amount of crosslinking agent is control glutaraldehyde
The 0.05-0.2% that quality is polyvinyl alcohol and mixed solution of sodium alginate quality is added
8. according to the method described in claim 3, it is characterized in that it is 6-24h that mixing time after crosslinking agent is added in step (2).
9. according to the method described in claim 3, it is characterized in that crosslinking agent described in step (3) is glutaraldehyde, maleic acid
Or citric acid；The addition quality of crosslinking agent is the 0.05-1.7% of PVA solution quality；It is acid through (1) treated in step (3)
The molar ratio of catalyst loading and polyvinyl alcohol (PVA) are 0.1-0.3；Step is put into straight alcohol solution described in (3)
Soaking time is 0.5-2h.
10. according to the method described in claim 3, it is characterized in that the knifing rate in step (2) and (3) is 5-30m
min-1；The height that scraper is adjusted in step (2) and step (3) is 200-700 μm.
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